U.S. patent application number 13/771569 was filed with the patent office on 2013-10-03 for processes for producing vinyl acetate composition having low impurity content.
The applicant listed for this patent is CELANESE INTERNATIONAL CORPORATION. Invention is credited to Naveed Aslam, Jessica Freeman, Ilias S. Kotsianis, Lauren Moore, Quiang Yao.
Application Number | 20130261330 13/771569 |
Document ID | / |
Family ID | 49235883 |
Filed Date | 2013-10-03 |
United States Patent
Application |
20130261330 |
Kind Code |
A1 |
Aslam; Naveed ; et
al. |
October 3, 2013 |
Processes for Producing Vinyl Acetate Composition Having Low
Impurity Content
Abstract
The present invention, in one embodiment, is to a process for
inhibiting impurity formation a vinyl acetate formation reaction.
The process comprises the step of providing a reactor comprising an
inlet section, an outlet section, a filler (or fillers), and a
catalyst block section. The filler is disposed in the outlet
section. The catalyst block section may be in communication with
and configured between the inlet and outlet sections. The process
further comprises the steps of introducing the reactants to the
inlet section and contacting the reactants in the catalyst block
section under conditions effective to form a crude vinyl acetate
composition. The process may further comprise the step of directing
the crude vinyl acetate composition into the outlet section, which
comprises the filler.
Inventors: |
Aslam; Naveed; (Pasadena,
TX) ; Freeman; Jessica; (Pasadena, TX) ;
Kotsianis; Ilias S.; (Houston, TX) ; Moore;
Lauren; (Webster, TX) ; Yao; Quiang; (Baton
Rouge, LA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CELANESE INTERNATIONAL CORPORATION |
Irving |
TX |
US |
|
|
Family ID: |
49235883 |
Appl. No.: |
13/771569 |
Filed: |
February 20, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61617325 |
Mar 29, 2012 |
|
|
|
61614947 |
Mar 23, 2012 |
|
|
|
Current U.S.
Class: |
560/241 ;
422/129 |
Current CPC
Class: |
C07C 67/05 20130101;
C07C 69/15 20130101; B01J 19/00 20130101; B01J 8/025 20130101; C07C
67/05 20130101; B01J 2208/025 20130101 |
Class at
Publication: |
560/241 ;
422/129 |
International
Class: |
C07C 67/05 20060101
C07C067/05; B01J 19/00 20060101 B01J019/00 |
Claims
1. A process for inhibiting impurity formation in a vinyl acetate
reaction, the process comprising: (a) providing a reactor
comprising an inlet section, an outlet section, a filler in the
outlet section, and a catalyst block section in communication with
and configured between the inlet and outlet sections; (b)
introducing reactants comprising acetic acid, oxygen, and ethylene
to the inlet section; (c) contacting the reactants in the catalyst
block section under conditions effective to form a crude vinyl
acetate composition; and (d) directing the crude vinyl acetate
composition into the outlet section.
2. The process of claim 1, wherein the crude vinyl acetate
composition exiting the outlet section comprises less than 2,000
wppm impurities.
3. The process of claim 1, wherein the outlet section comprises a
housing defining an outlet chamber and the filler is disposed
within the outlet chamber.
4. The process of claim 3, wherein the outlet section comprises at
least one outlet line for directing the crude vinyl acetate
composition from the outlet chamber and the filler is disposed in
the at least one outlet line.
5. The process of claim 4, wherein the filler is attached to at
least one of an interior of the housing or a wall of the outlet
line.
6. The process of claim 1, wherein the oxygen and the ethylene are
combined prior to step (b) in a combined inlet line.
7. The process of claim 1, wherein the filler is provided at a
loading factor ranging from 0.001 to 0.8.
8. The process of claim 1, wherein the pressure in the outlet
section ranges from 0.1 MPa to 10 MPa.
9. The process of claim 1, wherein the filler is selected from the
group consisting of glass, zeolites, silica, zirconium oxide, and
mixtures thereof.
10. The process of claim 1, wherein the filler comprises stainless
steel.
11. A process for producing a vinyl acetate composition, the
process comprising: (a) providing a reactor comprising an inlet
section, an outlet section, a filler in either or both of the inlet
section and the outlet section, and a catalyst block section in
communication with and configured between the inlet and outlet
sections; (b) introducing reactants comprising acetic acid, oxygen,
and ethylene to the inlet section; (c) contacting the reactants in
the catalyst block section under conditions effective to form a
crude vinyl acetate composition; and (d) directing the crude vinyl
acetate composition into the outlet section.
12. A reactor for forming vinyl acetate comprising: an inlet
section for receiving reactants, an outlet section for exiting a
crude vinyl acetate composition; a catalyst block section in
communication with and configured between the inlet and outlet
sections for catalyzing a reaction to form a crude vinyl acetate
composition; and a filler disposed in at least a portion of the
outlet section to form a filled outlet section.
13. The reactor of claim 12, wherein the outlet section comprises a
housing defining an outlet chamber and the filler is disposed
within the outlet chamber.
14. The reactor of claim 12, wherein the outlet section comprises
at least one outlet line for directing the crude vinyl acetate
composition from the outlet chamber and the filler is disposed in
the at least one outlet line.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to U.S. Provisional
Patent Application No. 61/617,325, filed Mar. 29, 2012, and to U.S.
Provisional Patent Application No. 61/614,947, filed Mar. 23, 2012,
the entire contents and disclosure of which are hereby incorporated
by reference.
FIELD OF THE INVENTION
[0002] This invention relates to processes for producing vinyl
acetate and, in particular, to improved processes for producing
vinyl acetate, which reduce the amount vinyl acetate impurities in
the vinyl acetate product.
BACKGROUND OF THE INVENTION
[0003] Vinyl acetate is an important monomer in the production of
polyvinyl acetate and polyvinyl alcohol products. Vinyl acetate is
conventionally prepared by contacting acetic acid and ethylene with
molecular oxygen to form a crude vinyl acetate composition. The
reaction is typically conducted in the presence of a suitable
catalyst, which may comprise palladium, an alkali metal acetate
promoter, and, optionally, a co-promoter, e.g., gold or cadmium, on
a catalyst support. U.S. Pat. No. 6,696,596, for example, indicates
that it is well known to manufacture vinyl acetate in a reaction in
the gas phase with acetic acid and oxygen or oxygen containing
gasses over fixed-bed catalysts. U.S. Pat. No. 6,040,474, as
another example, describes the manufacture of acetic acid and/or
vinyl acetate using two reaction zones wherein the first reaction
zone comprises ethylene and/or ethane for oxidation to acetic acid
with the second reaction zone comprising acetic acid and ethylene
with the product streams being subsequently separated thereby
producing vinyl acetate. Also, U.S. Pat. No. 6,476,261 describes an
oxidation process for the production of alkenes and carboxylic
acids such as ethylene and acetic acid, which are reacted to form
vinyl acetate, demonstrating that more than one reaction zone can
be used to form the vinyl acetate.
[0004] In addition, U.S. Pat. No. 6,013,834 discloses a process for
the production of vinyl acetate by reaction in the vapor phase of
ethylene, oxygen and acetic acid as reactants, comprising passing
at a temperature sufficient to initiate the reaction, a feed gas
comprising said reactants and continuously or intermittently
containing liquid acetic acid and/or non-volatile components,
through a filter and distribution bed of inert material having
throughout its volume substantial intercommunicating open spaces
among the solid portions, and thence through a plurality of tubes
each containing a bed of catalyst for the reaction, and withdrawing
a product gas comprising VA. The filter and distribution bed acts
to filter out the liquid acetic acid and/or non-volatile components
and distribute more evenly the feed gas into the tubes.
[0005] This vinyl acetate reaction, however, lends itself to the
production of several unwanted impurities, including, for example,
non-volatile residues such as polymerized vinyl acetate,
polymerized ethylene, and heavy ends, such as acetoxyacetic acid.
The formation of these impurities is detrimental in many respects.
For example, the formation of these impurities reduces vinyl
acetate yield and may lead to fouling of vinyl acetate production
equipment, e.g., purification towers and vaporizers.
[0006] Conventionally, a heavy ends tower is utilized to remove
these impurities. The heavy ends tower, however, is expensive.
Also, the level of purification achieved by the heavy ends tower
leaves much to be desired. Thus, the need exists for methods for
producing a vinyl acetate composition wherein the formation of
impurities is inhibited or wherein the impurity content is
reduced.
[0007] The references mentioned above are hereby incorporated by
reference.
SUMMARY OF THE INVENTION
[0008] The present invention, in one embodiment, is to a process
for inhibiting impurity formation a vinyl acetate formation
reaction. The process comprises the step of providing a reactor
comprising an inlet section, an outlet section, a filler (or
fillers), and a catalyst block section. The filler may be disposed
in the outlet section. The catalyst block section may be in
communication with and configured between the inlet and outlet
sections. In one embodiment, the outlet section comprises at least
one outlet line for conveying the crude reaction mixture from the
outlet chamber. In these cases, the filler may be disposed in the
at least one outlet line. The process further comprises the steps
of introducing the reactants to the inlet section and contacting
the reactants in the catalyst block section under conditions
effective to form a crude vinyl acetate composition. The crude
vinyl acetate composition, as formed, may comprise vinyl acetate
(monomer), residual acetic acid, residual oxygen, water, and,
optionally, residual ethylene (monomer), and an initial amount of
impurities, e.g., peroxides, non-volatile residues ("NVR"), heavy
ends, light ends and/or mixtures thereof. The process may further
comprise the step of directing the crude vinyl acetate composition
into the outlet section, which comprises the filler.
[0009] As a result of use of the filler in the outlet section, the
crude vinyl acetate composition that exits the outlet section
comprises small amounts, if any, impurities, e.g., less than 2,000
wppm impurities.
BRIEF DESCRIPTION OF DRAWINGS
[0010] The invention is described in detail below with reference to
the appended drawings, wherein like numerals designate similar
parts.
[0011] FIG. 1 is a schematic diagram of an exemplary vinyl acetate
production process, which includes reaction and separation
according to one embodiment of the present invention.
[0012] FIG. 2 is a schematic diagram of an exemplary vinyl acetate
reactor showing an inlet section, a catalyst block section, filler,
and an outlet section according to one embodiment of the present
invention.
[0013] FIG. 3 is a cross sectional view of an outlet line according
to one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Introduction
[0014] Conventional vinyl acetate processes suffer from the
production of unwanted impurities. Some of these impurities include
light ends, non-volatile residues ("NVR"), e.g., polymerized
monomers, heavy ends, methane, ethane, carbon monoxide, inerts,
carbon dioxide, and ethyl acetate, which reduce yield and have
detrimental effects on production equipment. Examples of affected
production equipment include purification towers and vaporizers. As
a result, significant resources must be devoted to remove these
impurities from the crude vinyl acetate composition.
[0015] For example, some unwanted non-volatile residues ("NVR") may
be formed via the polymerization of monomers such as ethylene and
vinyl acetate. As another example, oxygen and/or peroxides that are
present in and around the reactor may promote the formation of
undesirable heavy ends. Exemplary heavy ends include ethylene
glycol, ethylidene diacetate, ethylene glycol monoacetate, vinyl
acetoxy acetate, ethylene glycol diacetate, cis-diacetoxy ethylene,
trans-diacetoxy ethylene, glycolic acid, acetoxyacetic acid, and
mixtures thereof.
[0016] Without being bound by theory, it is believed that
polymerization of monomers may be induced by the presence of
radicals, e.g., oxygen radicals. Typically, oxidation of vinyl
acetate and/or ethylene is a chain reaction. As such, the
interruption of the chain reaction(s) may significantly inhibit the
formation of detrimental impurities. In addition, by limiting
contact between the vinyl acetate monomers, residual ethylene
monomers and/or oxygen/oxygen radicals, the formation of
detrimental impurities may be inhibited or eliminated.
[0017] It has now been discovered that chain oxidation reactions
and/or monomer contact may be beneficially inhibited by employing a
filler in the spaces where oxygen and/or oxygen radicals and
monomers are present with one another. As a result, fewer
impurities are produced, and the need for removal of impurities in
the purification system is reduced or eliminated. Accordingly,
production efficiencies may be improved. For example, impurity
monitoring and/or removal equipment could be eliminated.
[0018] Accordingly, the present invention relates to the inhibition
of the formation of vinyl acetate impurities and/or to the
reduction of vinyl acetate impurity content in a vinyl acetate
composition. In one embodiment, the reactants comprise a reaction
mixture of acetic acid, oxygen, and ethylene. The process comprises
the step of providing a reactor comprising an inlet section, an
outlet section, a filler or a plurality of fillers, and a catalyst
block section. The inventive process further comprises the steps of
introducing the reactants, e.g., the reaction mixture, to the inlet
section and contacting the reactants in the catalyst block section
under conditions effective to form the crude vinyl acetate
composition and directing the crude vinyl acetate composition into
the outlet section. The catalyst block section is in communication
with and configured between the inlet and outlet sections. The
catalyst block section comprises a catalyst that catalyzes a
reaction of the acetic acid, the oxygen, and the ethylene to form a
crude vinyl acetate composition. The crude vinyl acetate
composition comprises, inter alia, vinyl acetate monomer, residual
ethylene monomer and/or oxygen, e.g., residual oxygen and/or oxygen
radicals. In one embodiment, the filler is disposed in at least a
portion of the outlet section. By disposing the filler in the
outlet section, contact between 1) the ethylene and/or vinyl
acetate monomers and/or 2) monomers and the oxygen and/or oxygen
radicals is reduced and the potential chain reaction that may form
impurities is advantageously inhibited or eliminated.
[0019] In one embodiment, the resultant crude vinyl acetate
composition exiting the outlet section of the reactor comprises
vinyl acetate and optionally little, if any, impurities, e.g., less
than 2,000 wppm impurities, e.g., less than 1,000 wppm, less than
500 wppm, less than 250 wppm or less than 100 wppm. In terms of
ranges, the crude vinyl acetate composition optionally comprises
from 0 wppm to 2,000 wppm impurities, e.g., from 100 wppm to 1,000
wppm or from 250 wppm to 1,000 wppm. In another embodiment, the
inhibited amount of impurities is less than the amount of
impurities that would be present had the filler not been employed,
e.g., at least 10% less than, at least 25% less than, or at least
40% less than. The crude vinyl acetate composition may further
comprise residual acetic acid and water. Exemplary weight
percentage ranges for these components, and other exemplary
components, are shown in Table 1 below.
[0020] In one embodiment, the filler comprises an inert material,
which may be selected from the group consisting of glass, zeolites,
silica, and zirconium oxide. In one embodiment, the filler may be
selected from the group consisting of alumina, silica-alumina,
titania, zirconia, silicates, aluminosilicates, titanates, spinel,
silicon carbide, carbon, and mixtures thereof. The filler may be
gas permeable in order to allow the reactants to pass therethrough,
and may include a porous network for this purpose. In one
embodiment, the size and shape of the filler particles is selected
such that a predetermined porosity is achieved. In one embodiment,
the average porosity ranges from 0.2 to 0.6, e.g., from 0.3 to 0.5.
Other porosity ranges, however, are considered to be within the
contemplation of the invention. Porosity is a measurement of voids,
e.g., empty spaces, present in the filler. As one example, porosity
may be a ratio of the volume of voids and the total volume of the
filler. In some embodiments, the size and shape of the filler
particles may be selected so as to avoid significantly affecting
the pressure drop across the filler bed or the reactor bed.
[0021] In another aspect, the filler comprises particles, pellets
or beads of a filler material and the porous network is formed by
the voids between adjacent particles, pellets or beads. In one
embodiment, the filler particles are spherical in shape. In another
embodiment, the filler comprises stainless steel, e.g., steel
wool.
[0022] The process may further comprise the step of purifying the
crude vinyl acetate composition in a purification system to produce
a purified vinyl acetate composition. An exemplary separation zone
is described below and in FIG. 1.
[0023] In one embodiment, the filler inhibits impurity formation by
reducing contact between the oxygen and the ethylene, each of which
may be present in the crude vinyl acetate composition. In another
embodiment, the filler inhibits impurity formation after the vinyl
acetate reaction has taken place in the catalyst block section. In
this embodiment, the filler reduces contact between the oxygen and
the formed vinyl acetate (and optionally residual ethylene) to
inhibit impurity formation. In one embodiment, the filler is
disposed in both the inlet section and the outlet section. In these
embodiments, impurity inhibition is achieved both leading up to the
reaction zone, i.e., the catalyst block section, and after the
reaction has taken place. Thus, the processes of the present
invention beneficially improve vinyl acetate yield and reduce or
eliminate the problems caused by the presence of impurity in the
purification equipment.
Acetoxylation of Ethylene
[0024] As shown FIG. 1, in some embodiments, oxygen and ethylene
are fed to reactor 100 via feed lines 102 and 104, respectively.
Acetic acid may be fed to vaporizer 106 via feed stream 108.
Vaporized acetic acid exits vaporizer 106 and is directed to
reactor 100 via line 110. The vinyl acetate formation reaction
takes place in reactor 100. The crude vinyl acetate stream exits
reactor 100 as an effluent stream via line 112. FIG. 1 is further
discussed below.
[0025] FIG. 2 shows reactor 200, which comprises inlet section 202,
outlet section 204, and catalyst block section 206. Catalyst block
section 206, which may comprise a catalyst bed, is configured
between inlet section 202 and outlet section 204. Inlet section 202
is in communication with catalyst block section 206, which, in
turn, is in communication with outlet section 204. As such, the
reactants may be conveyed through inlet section 202 to catalyst
block section 206, where the vinyl acetate reaction occurs. The
reaction yields a crude vinyl acetate composition, which is
directed from catalyst block section 206 through outlet section
204.
[0026] In one embodiment, inlet section 202 comprises inlet housing
208, which defines inlet chamber 210. Inlet chamber 210 may be
enclosed by walls of inlet section housing 208. In addition, inlet
section 202 may also comprise at least one inlet line 212 for
conveying reactants from an outside source to inlet chamber 210. In
one embodiment, the acetic acid, oxygen, and ethylene are combined
to form a reaction mixture and the reaction mixture is conveyed to
inlet chamber 210 via inlet line 212. In another embodiment (not
shown), inlet section 202 comprises a plurality of inlet lines. As
an example, there may be a separate inlet line for each reactant.
In one embodiment, the oxygen and the ethylene are combined prior
to being introduced to inlet section 202. In such a case, a
combined inlet line would be formed. As noted above, the outlet
section comprises filler 250. In some embodiments, the filler is
disposed in the inlet section as well. For example the filler may
be disposed in at least a portion of inlet chamber 210 and/or in
one or more inlet lines 212 and/or in the combined inlet line. In
one embodiment, the filler 250 is disposed in both inlet chamber
210 and in at least one of inlet lines 212.
[0027] In some embodiments, the one or more filler 250 are disposed
in at least a portion of inlet chamber 210, e.g., at least 25 vol.
% of inlet chamber 210, at least 50 vol. %, at least 80 vol. % or
at least 95 vol. % of inlet chamber 210.
[0028] Outlet section 204 may comprise outlet housing 214, which
defines outlet chamber 216. Outlet chamber 216 may be enclosed by
walls of outlet housing 214. In addition, outlet section 204 may
also comprise at least one outlet line 218 for conveying the crude
vinyl acetate composition from outlet chamber 216 for further
processing or storage. In some embodiments, the filler 250 is
disposed in at least a portion of outlet chamber 216, e.g., at
least 25 vol. % of outlet chamber 216, at least 50 vol. %, at least
80 vol. % or at least 95 vol. % of outlet chamber 216. In another
embodiment, the one or more filler 250 is disposed in at least a
portion of at least one of the outlet lines 212. In one embodiment,
the one or more filler 250 is disposed in both outlet chamber 216
and in at least one of outlet lines 218.
[0029] In one embodiment, the filler may be configured loosely in
either or both of the inlet and/or outlet section. In another
embodiment, as shown in FIG. 3, the filler 350 may be disposed in
either or both the inlet line and/or outlet line, optionally in the
outlet line. For example, the filler may be loosely packed into the
inlet line and/or the outlet line. In another embodiment, the
filler may be attached to an interior of the housing and/or to wall
302 of an inlet line and/or an outlet line. In another embodiment,
the filler may be disposed in either or both the inlet section
and/or the outlet section at a loading factor, B, as defined below,
ranging from 0.001 to 0.8, e.g., from 0.001 to 0.5, or from 0.01 to
0.5. In terms of lower limits, the loading factor may be at least
0.001, e.g., at least 0.01 or at least 0.05. In terms of upper
limits, the loading factor may be less than 0.8, e.g., less than
0.5 or less than 0.4. If the loading factor is too large, the
pressure drop across the respective housing or line may have a
tendency to accelerate the ethylene/vinyl acetate oxidation chain
reactions undesirably causing the formation of impurities. For
example, without being bound by theory, the concentration of the
polymer precursors may increase if the loading factor is too high,
which would may promote polymerization rather than inhibit
polymerization. Conversely, if the loading is too small, the
inhibiting effect of the filler may be reduced.
[0030] In one embodiment, the loading factor, B, is defined by the
following formula.
B=PD/PS [0031] wherein PD is the pressure drop per unit length
(Pa/m) under operating conditions; and [0032] PS is the ratio of
mass flow (kg/s) to volume flow (m.sup.3/s), of all components
under operating conditions, multiplied by 9.81 (m/s).
[0033] The filler may generally comprise a wide variety of
materials. In one embodiment, the filler comprises materials that
are inert or substantially inert. As one example, the filler is
resistant to reactions with the reactants, e.g., acetic acid,
ethylene, oxygen, and water, as well as to vinyl acetate itself.
For example, aluminum may react with the acetic acid. As a result,
if a composition comprising aluminum is employed as the filler, the
composition should comprise lower amounts of aluminum, e.g., less
than 90 wt % or less than 80 wt %. Exemplary filler materials
include glass, zeolites, silica, stainless steel, aluminum (in
lower amounts), zirconium oxide and mixtures thereof. The one or
more filler may be attached or retained in the reactor and/or inlet
or outlet lines using mechanical fasteners, adhesives, welding,
and/or screening. Of course, this listing is merely exemplary and
other retaining mechanisms are well within the contemplation of the
invention. In one embodiment, the filler is stainless steel and the
stainless steel filler is loosely packed in the inlet and outlet
chambers. In another embodiment, the filler is glass and the glass
is adhesively bonded to the wall of the inlet and outlet lines. In
one embodiment, the filler is packed into the bed of the
reactor.
[0034] The shape of the filler may vary widely. In one embodiment,
the filler is spherical in shape. In another embodiment, the filler
is cubic or cylindrical in shape. In one embodiment, the filler
comprises spherical pellets, optionally stainless steel spherical
pellets or glass spheres.
[0035] In addition to being unreactive, the filler material also
may be characterized in terms of mechanical or physical properties,
e.g., tensile strength or crush strength. Thus, filler having high
strength, e.g., stainless steel, may be particularly
beneficial.
Vinyl Acetate Composition
[0036] The specific composition of the crude vinyl acetate
composition may vary widely depending, for example, on the reaction
conditions and catalyst employed. Some exemplary compositions for
the crude vinyl acetate composition are presented in Table 1. These
compositions are based on a crude vinyl acetate composition
prepared in a reactor comprising filler disposed in the inlet
section and/or in the outlet section.
TABLE-US-00001 TABLE 1 Crude Vinyl Acetate Compositions Component
Conc. (wt. %) Conc. (wt. %) Conc. (wt. %) Vinyl Acetate 1 to 75 1
to 50 2 to 35 Acetic Acid 1 to 80 1 to 50 5 to 25 Impurities 0 to
2,000 100 to 1,000 250 to 1,000 wppm wppm wppm Ethylene 10 to 90 10
to 50 20 to 40 Ethane 1 to 40 1 to 20 5 to 15 Water 1 to 20 1 to 10
2 to 8 Carbon Dioxide 1 to 75 1 to 50 2 to 35
[0037] As shown in Table 1, as a result of the filler being
disposed in the outlet section of the reactor, the crude vinyl
acetate composition that is formed comprises a major amount of
vinyl acetate and, beneficially, a low amount of impurities, if
any. Because of these low amounts of resultant impurities, the need
for additional separation processes and units to remove same is
minimized or eliminated. In one embodiment, a "major amount" refers
to an amount greater than 50 wt %, e.g., greater than 60 wt % or
greater than 70 wt %. Weight percentage ranges for other components
that may be present in the crude vinyl acetate are presented in
Table 1.
[0038] The reactors utilized in conventional vinyl acetate
production processes have not utilized filler in the outlet
sections to inhibit impurity formation. As such, the crude vinyl
acetate compositions, as formed, contain significantly higher
amounts of impurities. Thus, surprisingly and unexpectedly, the
formed vinyl acetate compositions of the present invention
beneficially comprise lower amounts of impurities than conventional
systems. In some embodiments, for example, the reaction system of
the invention forms at least 10% less impurities than an analogous
system, run under the same conditions, but without using any
filler, e.g., at least 25 wt. % less impurities or at least 25 wt.
% impurities.
Vinyl Acetate Formation
[0039] The features of the present invention may be applied to any
suitable vinyl acetate production process. As noted above, the
formation of vinyl acetate may be carried out by reacting acetic
acid and ethylene in the presence of oxygen. In other embodiments,
the inventive use of the filler may apply to production of other
monomers such as, for example, acrylic acid, vinyl esters, or
diacetoxyethylene. This reaction may take place heterogeneously
with the reactants being present in the gas phase. The reactor may
be configured such that the reactor is capable of removing heat
from the reaction. Suitable reactor types include, but are not
limited to, a fixed bed reactor and a fluidized bed reactor. In one
embodiment, the molar ratio of ethylene to acetic acid in the
reaction ranges from 1:1 to 10:1, e.g., from 1:1 to 5:1; or from
2:1 to 3:1. In one embodiment, the molar ratio of ethylene to
oxygen in the reaction ranges from 1:1 to 20:1, e.g., from 1.5:1 to
10:1; or from 2:1 to 5:1. In another embodiment, the molar ratio of
acetic acid to oxygen in the reaction ranges from 1:1 to 10:1,
e.g., from 1:1 to 5:1; or from 1:1 to 3:1.
[0040] The raw materials, e.g., acetic acid, used in connection
with the process of this invention may be derived from any suitable
source including natural gas, petroleum, coal, biomass, and so
forth. For purposes of the present invention, acetic acid may be
produced using a methanol feed via methanol carbonylation as
described in U.S. Pat. Nos. 7,208,624; 7,115,772; 7,005,541;
6,657,078; 6,627,770; 6,143,930; 5,599,976; 5,144,068; 5,026,908;
5,001,259; and 4,994,608, the entire disclosures of which are
incorporated herein by reference. Optionally, the production of
ethanol may be integrated with such methanol carbonylation
processes.
[0041] As petroleum and natural gas prices fluctuate becoming
either more or less expensive, methods for producing acetic acid
and intermediates such as methanol and carbon monoxide from
alternate carbon sources have drawn increasing interest. In
particular, when petroleum is relatively expensive, it may become
advantageous to produce acetic acid from synthesis gas ("syngas")
that is derived from more available carbon sources. U.S. Pat. No.
6,232,352, the entirety of which is incorporated herein by
reference, for example, teaches a method of retrofitting a methanol
plant for the manufacture of acetic acid. By retrofitting a
methanol plant, the large capital costs associated with CO
generation for a new acetic acid plant are significantly reduced or
largely eliminated. All or part of the syngas is diverted from the
methanol synthesis loop and supplied to a separator unit to recover
CO, which is then used to produce acetic acid. In a similar manner,
hydrogen for the hydrogenation step may be supplied from
syngas.
[0042] In some embodiments, some or all of the raw materials may be
derived partially or entirely from syngas. For example, the acetic
acid may be formed from methanol and carbon monoxide, both of which
may be derived from syngas. The syngas may be formed by partial
oxidation reforming or steam reforming, and the carbon monoxide may
be separated from syngas. Similarly, hydrogen that is used in the
step of hydrogenating the acetic acid to form the crude ethanol
product may be separated from syngas. The syngas, in turn, may be
derived from variety of carbon sources. The carbon source, for
example, may be selected from the group consisting of natural gas,
oil, petroleum, coal, biomass, and combinations thereof. Syngas or
hydrogen may also be obtained from bio-derived methane gas, such as
bio-derived methane gas produced by landfills or agricultural
waste.
[0043] In another embodiment, in addition to the acetic acid formed
via methanol carbonylation, some additional acetic acid may be
formed from the fermentation of biomass and may be used in the
hydrogenation step. The fermentation process may utilize an
acetogenic process or a homoacetogenic microorganism to ferment
sugars to acetic acid producing little, if any, carbon dioxide as a
by-product. The carbon efficiency for the fermentation process may
be greater than 70%, greater than 80% or greater than 90% as
compared to conventional yeast processing, which typically has a
carbon efficiency of about 67%. Optionally, the microorganism
employed in the fermentation process is of a genus selected from
the group consisting of Clostridium, Lactobacillus, Moorella,
Thermoanaerobacter, Propionibacterium, Propionispera,
Anaerobiospirillum, and Bacteriodes, and in particular, species
selected from the group consisting of Clostridium formicoaceticum,
Clostridium butyricum, Moorella thermoacetica, Thermoanaerobacter
kivui, Lactobacillus delbrukii, Propionibacterium acidipropionici,
Propionispera arboris, Anaerobiospirillum succinicproducens,
Bacteriodes amylophilus and Bacteriodes ruminicola. Optionally in
this process, all or a portion of the unfermented residue from the
biomass, e.g., lignans, may be gasified to form hydrogen that may
be used in the hydrogenation step of the present invention.
Exemplary fermentation processes for forming acetic acid are
disclosed in U.S. Pat. Nos. 6,509,180; 6,927,048; 7,074,603;
7,507,562; 7,351,559; 7,601,865; 7,682,812; and 7,888,082, the
entireties of which are incorporated herein by reference. See also
U.S. Pub. Nos. 2008/0193989 and 2009/0281354, the entireties of
which are incorporated herein by reference.
[0044] Examples of biomass include, but are not limited to,
agricultural wastes, forest products, grasses, and other cellulosic
material, timber harvesting residues, softwood chips, hardwood
chips, tree branches, tree stumps, leaves, bark, sawdust, off-spec
paper pulp, corn, corn stover, wheat straw, rice straw, sugarcane
bagasse, switchgrass, miscanthus, animal manure, municipal garbage,
municipal sewage, commercial waste, grape pumice, almond shells,
pecan shells, coconut shells, coffee grounds, grass pellets, hay
pellets, wood pellets, cardboard, paper, plastic, and cloth. See,
e.g., U.S. Pat. No. 7,884,253, the entirety of which is
incorporated herein by reference. Another biomass source is black
liquor, a thick, dark liquid that is a byproduct of the Kraft
process for transforming wood into pulp, which is then dried to
make paper. Black liquor is an aqueous solution of lignin residues,
hemicellulose, and inorganic chemicals.
[0045] U.S. Pat. No. RE 35,377, also incorporated herein by
reference, provides a method for the production of methanol by
conversion of carbonaceous materials such as oil, coal, natural gas
and biomass materials. The process includes hydrogasification of
solid and/or liquid carbonaceous materials to obtain a process gas
which is steam pyrolized with additional natural gas to form
syngas. The syngas is converted to methanol which may be
carbonylated to acetic acid. The method likewise produces hydrogen
which may be used in connection with this invention as noted above.
U.S. Pat. No. 5,821,111, which discloses a process for converting
waste biomass through gasification into syngas, and U.S. Pat. No.
6,685,754, which discloses a method for the production of a
hydrogen-containing gas composition, such as syngas including
hydrogen and carbon monoxide, are incorporated herein by reference
in their entireties.
[0046] The acetic acid fed to the reaction may also comprise other
carboxylic acids and anhydrides, as well as acetaldehyde and
acetone. In one embodiment, a suitable acetic acid feed stream
comprises one or more of the compounds selected from the group
consisting of acetic acid, acetic anhydride, acetaldehyde, ethyl
acetate, and mixtures thereof. These other compounds may also be
hydrogenated in the processes of the present invention. In some
embodiments, the presence of carboxylic acids, such as propanoic
acid or its anhydride, may be beneficial in producing propanol.
Water may also be present in the acetic acid feed.
[0047] Alternatively, acetic acid in vapor form may be taken
directly as crude product from the flash vessel of a methanol
carbonylation unit of the class described in U.S. Pat. No.
6,657,078, the entirety of which is incorporated herein by
reference. The crude vapor product, for example, may be fed
directly to the ethanol synthesis reaction zones of the present
invention without the need for condensing the acetic acid and light
ends or removing water, saving overall processing costs.
[0048] Although carbonylation may be an optional acetic acid
production method, other suitable methods may be employed. In one
embodiment that employs carbonylation, the carbonylation system
optionally comprises a reaction zone, which includes a reactor, a
flasher and optionally a reactor recovery unit. In one embodiment,
carbon monoxide is reacted with methanol in a suitable reactor,
e.g., a continuous stirred tank reactor ("CSTR") or a bubble column
reactor. In one embodiment, the carbonylation process is a low
water, catalyzed, e.g., rhodium-catalyzed, carbonylation of
methanol to acetic acid, as exemplified in U.S. Pat. No. 5,001,259,
which is hereby incorporated by reference.
[0049] The ethylene similarly may be produced by any suitable
method. In one embodiment, the ethylene is formed via the
hydrogenation of acetic acid followed by the dehydration of the
acetic acid to form ethylene. As another alternative, the acetic
acid and the ethylene may be produced via oxidation of an alkane,
e.g., ethane, as discussed in U.S. Pat. No. 6,476,261, the
disclosure of which is hereby incorporated by reference. The oxygen
used in the formation of vinyl acetate in the method of the present
invention may further comprise other inert gases such as nitrogen.
As one example, the oxygen used in the vinyl acetate reaction is
provided by an air stream.
[0050] In one embodiment, additional ethylene may be fed to the
reactor. This additional ethylene, as well as the reactant ethylene
mentioned above, may be substantially pure. In one embodiment, the
ethylene may be admixed, for example, with one or more of nitrogen,
methane, carbon dioxide, carbon monoxide, hydrogen, and low levels
of C.sub.3/C.sub.4 alkenes/alkanes. Additional oxygen may be fed to
the reactor. The additional oxygen, if used, may be air or a gas
richer or poorer in molecular oxygen than air. One suitable
additional molecular oxygen-containing gas may be, oxygen diluted
with a suitable diluent, for example nitrogen or carbon dioxide. In
one embodiment, the additional molecular oxygen-containing gas is
oxygen. In one embodiment, at least some of the oxygen is fed to
the reactor independently from the ethylene and acetic acid.
[0051] The vinyl acetate reaction may suitably be carried out at a
temperature in the range of from 100.degree. C. to 300.degree. C.,
e.g., from 140.degree. C. to 220.degree. C. or from 150.degree. C.
to 200.degree. C. In another embodiment, the reaction may be
carried out pressure in the range of from 0.1 MPa to 10 MPa, e.g.,
from 0.1 MPa to 2.5 MPa or from 1 MPa to 2.5 MPa.
[0052] In one embodiment, the reaction is conducted over a
catalyst. Suitable catalysts include catalysts comprising a first
metal and optionally one or more of a second metal, a third metal,
or additional metals. The catalyst optionally comprises a catalyst
support. The first and optional second and third metals may be
selected from palladium, gold, boron, alkali metals, and Group IB
or VIIIB transition metals. Some metal combinations include
palladium/gold and palladium/boron.
[0053] The first metal optionally is present in an amount from 0.1
to 10 wt. %, e.g., from 0.2 to 5 wt. %, or from 0.2 to 2.5 wt. %.
The additional metals, if present, may be present in amounts
ranging from 0.1 to 10 wt. %, e.g., from 0.2 to 5 wt. %, or from
0.2 to 2.5 wt. %. In other embodiments, the catalyst may comprise
metalloids, e.g., boron, in amounts ranging from 0.01 wt. % to 1
wt. %, e.g., from 0.01 wt. % to 0.2 wt. %. For catalysts comprising
two or more metals, the two or more metals may be alloyed with one
another. Alternatively, the two or more metals may comprise a
non-alloyed metal solution or mixture. Also, metal ratios may vary
depending on the metals used in the catalyst. If palladium and gold
are utilized, the ratio may range from 0.5:1 to 20:1, e.g., from
=1.8:1 to 10:1. In some exemplary embodiments where a first and
second metal are used, the mole ratio of the first metal to the
second metal is from 5:1 to 1:1, e.g., from 3:1 to 1:1, or from 2:1
to 1:1.
[0054] In addition to one or more metals, the exemplary catalysts
further comprise a support or a modified support, meaning a support
that includes a support material and a support modifier, which
adjusts the acidity of the support material. The total weight of
the support or modified support, based on the total weight of the
catalyst, may be from 75 wt. % to 99.9 wt. %, e.g., from 78 wt. %
to 97 wt. %, or from 80 wt. % to 95 wt. %. In some embodiments that
use a modified support, the support modifier is present in an
amount from 0.1 wt. % to 50 wt. %, e.g., from 0.2 wt. % to 25 wt.
%, from 0.5 wt. % to 15 wt. %, from 1 wt. % to 8 wt. %, from 1 wt.
% to 5 wt. %, or from 2 wt. % to 4 wt. %, based on the total weight
of the catalyst.
[0055] Suitable support materials may include silica, alumina,
silica-alumina, titania, ticano-silicates, zirconia,
zircono-silicate, niobia, silicates, alumino-silicates, titanates,
carbon, metals, and glasses. Possible supports include zirconia,
zircono-silicates, and titano-silicates. Suitable support modifiers
may include barium, magnesium, cerium, potassium, calcium, niobium,
tantalum, titanium, yttrium, strontium, zirconium, vanadium,
molybdenum, and rubidium. Possible support modifiers include
niobium, titanium, magnesium, and zirconium. In some embodiments,
the filler may comprise materials that are typically employed as
support materials, which include those materials listed above.
[0056] Specific examples of suitable catalysts include, for
example, those described in GB 1 559 5401; EP 0 330 853; EP 0 672
4563; U.S. Pat. Nos. 5,185,308; 5,691,267; 6,114,571; 6,852,877;
and 6,603,038. The disclosures of all of the above-mentioned
references are hereby incorporated by reference.
[0057] GB 1 559 540 describes suitable catalysts that can be
employed in the preparation of vinyl acetate by the reaction of
ethylene, acetic acid and oxygen. The catalysts are comprised of:
(1) a catalyst support having a particle diameter of from 3 to 7 mm
and a pore volume of from about 0.2 to 1.5 ml per gram, a 10% by
weight water suspension of the catalyst support having a pH from
about 3.0 to 9.0, (2) a palladium-gold alloy distributed in a
surface layer of the catalyst support, the surface layer extending
less than 0.5 mm from the surface of the support, the palladium in
the alloy being present in an amount of from about 1.5 to 5.0 grams
per liter of catalyst, and the gold being present in an amount of
from about 0.5 to 2.25 grams per liter of catalyst, and (3) from 5
to 60 grams per liter of catalyst of alkali metal acetate.
[0058] U.S. Pat. No. 5,185,308 describes a shell impregnated
catalyst active for the production of vinyl acetate from ethylene,
acetic acid, and an oxygen-containing gas, the catalyst consisting
essentially of (1) a catalyst support having a particle diameter
from about 3 to about 7 mm and a pore volume of 0.2 to 1.5 ml per
gram, (2) palladium and gold distributed in the outermost 1.0 mm
thick layer of the catalyst support particles, and (3) from about
3.5 to about 9.5% by weight of potassium acetate wherein the gold
to palladium weight ratio in said catalyst is in the range 0.6 to
1.25.
[0059] U.S. Pat. No. 5,691,267 describes a two step gold addition
method for a catalyst used in the gas phase formation of vinyl
acetate from the reaction of ethylene, oxygen, and acetic acid. The
catalyst is formed by (1) impregnating a catalyst carrier with
aqueous solutions of a water-soluble palladium salt and a first
amount of a water-soluble gold compound such as sodium-palladium
chloride and auric chloride, (2) fixing the precious metals on the
carrier by precipitating the water-insoluble palladium and gold
compounds by treatment of the impregnated carriers with a reactive
basic solution such as aqueous sodium hydroxide which reacts with
the palladium and gold compounds to form hydroxides of palladium
and gold on the carrier surface, (3) washing with water to remove
the chloride ion (or other anion), and (4) reducing all the
precious metal hydroxides to free palladium and gold, wherein the
improvement comprises (5) impregnating the carrier with a second
amount of a water-soluble gold compound subsequent to fixing a
first amount of water-soluble gold agent, and (6) fixing the second
amount of a water-soluble gold compound.
[0060] U.S. Pat. No. 6,114,571 describes a catalyst for forming
vinyl acetate in the gas phase from ethylene, acetic acid, and
oxygen or oxygen-containing gases wherein the catalyst is comprised
of palladium, gold, boron, and alkali metal compounds on a support.
The catalyst is prepared by a) impregnating the support with
soluble palladium and gold compounds; b) converting the soluble
palladium and gold compounds on the support into insoluble
compounds by means of an alkaline solution; c) reducing the
insoluble palladium and gold compounds on the support by means of a
reducing agent in the liquid phase; d) washing and subsequently
drying the support; e) impregnating the support with a soluble
alkali metal compound; and f) finally drying the support at a
maximum of 1500.degree. C., wherein boron or boron compounds are
applied to the catalyst prior to the final drying.
[0061] U.S. Pat. No. 6,603,038 describes a method for producing
catalysts containing metal nanoparticles on a porous support,
especially for gas phase oxidation of ethylene and acetic acid to
form vinyl acetate. The invention relates to a method for producing
a catalyst containing one or several metals from the group of
metals comprising the sub-groups Ib and VIIIb of the periodic table
on porous support particles, characterized by a first step in which
one or several precursors from the group of compounds of metals
from sub-groups Ib and VIIIb of the periodic table is or are
applied to a porous support, and a second step in which the porous,
optionally nanoporous support to which at least one precursor has
been applied is treated with at least one reduction agent, to
obtain the metal nanoparticles produced in situ in the pores of
said support.
[0062] EP 0 672 453 describes palladium-containing catalysts and
their preparation for fluid bed vinyl acetate processes.
[0063] An advantage of using a palladium-containing catalyst is
that any carbon monoxide produced in a prior reaction zone will be
consumed in the presence of oxygen and the palladium-containing
catalyst in the second reaction zone. An example of a prior
reaction zone is a reaction zone for preparing the reactants. This
eliminates the need for a separate carbon monoxide removal
reactor.
[0064] The vinyl acetate reaction may be characterized in terms of
conversions based on the reactants. In one embodiment, acetic acid
conversions range from 1% to 100%, e.g., from 5% to 50% or from 10%
to 45%. Oxygen conversions may range from 1% to 100%, e.g., from
20% to 100% or from 20% to 50%. Ethylene conversions may range from
1% to 90%, e.g., from 5% to 100% or from 10% to 50%. In one
embodiment, vinyl acetate selectivity, based on ethylene may range
from 20% to 100%, e.g., from 50% to 95% or from 75% to 90%.
[0065] In the vinyl acetate reaction, the catalyst may have a
productivity (measured in space time yield, STY) ranging from 10
g/hr-liter to 5,000 g/hr-liter, e.g., from 100 g/hr-liter to 2,000
g/hr-liter or from 200 g/hr-liter to 1,000 g/hr-liter, where
g/hr-liter means grams of vinyl acetate per hour per liter of
catalyst. In terms of upper limits, the space time yield maybe less
than 20,000 g/hr-liter, e.g., less than 10,000 g/hr-liter or less
than 5,000 g/hr-liter.
Separation
[0066] Returning to FIG. 1, the vinyl acetate production system
includes a separation zone to recover and/or purify the vinyl
acetate formed in reactor 100. Reactor effluent stream 112 is
directed to the separation zone. In one embodiment the separation
zone provides at least one derivative of reactor effluent 112. In
another embodiment, the derivative stream(s) of the reactor
effluent may be any stream that is yielded via the units of the
separation zone. In one embodiment, the derivative streams are
downstream of the reactor. Unreacted acetic acid in vapor form may
be cooled and condensed. The remainder of the crude vinyl acetate
composition in line 118, which is a derivative of the reactor
effluent, is directed to pre-dehydration column ("PDC") 120. In one
embodiment, the scavenger is added to line 118 via scavenger feed
line 114b. PDC 120 separates the contents of line 118 into a
residue comprising vinyl acetate and a distillate comprising vinyl
acetate, water, acetic acid, carbon monoxide, carbon dioxide, light
ends, heavy ends, and ethyl acetate. The vinyl acetate-containing
residue is directed to crude tank 122 via line 124. From crude tank
122, the vinyl acetate-containing residue may be stored and/or
directed to further processing.
[0067] The PDC distillate is optionally cooled, condensed, and
directed to an overhead phase separation unit, e.g., decanter 126,
via line 128, which is a derivative of the reactor effluent. In
some embodiments, the scavenger is added to line 128 via scavenger
feed line 114c. In one embodiment, the addition of the scavenger
occurs in the PDC or downstream thereof. Conditions are desirably
maintained in the process such that vapor contents of line 128,
once cooled, condensed, and directed to decanter 126, will separate
into a light phase and a heavy phase. Scavenger feed line 114c
shows addition of the scavenger after the cooling, however,
addition prior to cooling is easily within the contemplation of the
invention. Generally, line 128 is cooled to a temperature
sufficient to condense and separate the condensable components,
e.g., vinyl acetate, water, acetic acid, and other carbonyl
components, into an aqueous phase and an organic phase. The organic
phase exits decanter 126 via line 130. A portion of the organic
phase may be refluxed back to PDC 120, as shown by stream 132,
which is a derivative of the reactor effluent. In one embodiment,
the scavenger is added to line 132 via scavenger feed line 114d.
The aqueous phase exits decanter 126 and is directed via line 134
to further separation processing. As an example, line 134 may be
directed to decanter 146 of an azeotrope column 136. Lines 130 and
134 optionally may be combined, as shown, and directed to decanter
146 of azeotrope column 136.
[0068] Stream 128 may include carbon monoxide, carbon dioxide,
ethylene, ethane and other noncondensable gases, which may be
directed via stream 138 from decanter 126 to scrubber 140. Scrubber
140 removes, inter alia, carbon monoxide, carbon dioxide, and
hydrocarbons such as ethylene and ethane from stream 128. The
separated noncondensable components may be conveyed to further
processing, e.g., carbon dioxide removal, as shown by stream 142.
In another embodiment, at least a portion of stream 142 is recycled
bad to the reactor effluent or to heat exchange equipment
downstream of reactor 100, as shown by stream 142'. The residue
exiting scrubber 140 comprises vinyl acetate, water, and acetic
acid. The residue is yielded from scrubber 140 via line 144 and may
be combined with the vinyl acetate from line 124 prior to being
directed to crude tank 122.
[0069] From crude tank 122, the vinyl acetate is directed to
azeotrope column 136 via line 137, which is a derivative of the
reactor effluent. In one embodiment, the scavenger is added to line
137 via scavenger feed line 114e. In another embodiment the
addition of the scavenger occurs in azeotrope column 136 or
downstream thereof. Azeotrope column 136 separates line 137, which
comprises vinyl acetate, acetic acid, and water, into a distillate
stream in line 148 and a residue stream 149. Decanter 146 at the
top of azeotrope column 136 receives line 134, which comprises the
aqueous and organic phases from decanter 126. In addition, decanter
146 receives the distillate from azeotrope column 136. Azeotrope
column 136 separates line 137, which comprises vinyl acetate,
acetic acid, and water. The residue from azeotrope column 136
comprises acetic acid and water. This stream may be recycled back
to vaporizer 106 via line 149, or may be conveyed directly to
reactor 100 (not shown). The distillate from azeotrope column 136
comprises vinyl acetate and water and is directed to decanter 146,
e.g., a reflux decanter, via line 148. Decanter 146 separates at
least a portion of streams 134 and 148 into aqueous and organic
phases. The organic phase, which comprises vinyl acetate, exits
decanter 146 via line 152, which is a derivative of the reactor
effluent, and is directed to further processing. In one embodiment,
the scavenger is added to line 152 via scavenger feed line 114f. As
one example, line 152 is directed to dehydration column 154. The
aqueous phase exits decanter 146 via line 150. Line 150 (or a
portion thereof) may be refluxed back to azeotrope column 136.
[0070] Dehydration column 154 removes additional water from the
contents of line 152, thus yielding purified vinyl acetate via line
156. The water-containing distillate of dehydration column 154 may
be directed to overhead tank 158 via line 160. From overhead tank
158, line 162, which contains an amount of vinyl acetate, may be
returned to dehydration column 154. Line 164, which comprises water
and impurities may be directed to further processing, e.g., water
stripping. The residue of dehydration column 154 exits via line
166. The residue comprises various residuals, which may be recycled
or otherwise disposed.
EXAMPLES
[0071] While the invention has been described in detail,
modifications within the spirit and scope of the invention will be
readily apparent to those of skill in the art. In view of the
foregoing discussion, relevant knowledge in the art and references
discussed above in connection with the Background and Detailed
Description, the disclosures of which are all incorporated herein
by reference. In addition, it should be understood that aspects of
the invention and portions of various embodiments and various
features recited below and/or in the appended claims may be
combined or interchanged either in whole or in part. In the
foregoing descriptions of the various embodiments, those
embodiments which refer to another embodiment may be appropriately
combined with other embodiments as will be appreciated by one of
skill in the art. Furthermore, those of ordinary skill in the art
will appreciate that the foregoing description is by way of example
only, and is not intended to limit the invention.
* * * * *